Chlorination



May I3, 1930. c. CAMPI-BELL.

CHLORINATION l Filed June l5, 1927 NQRUTMQ SF Wunkuesu WN Patented May 13,1930

, UNITED STATES" PATENL'I OFFICE'.A

CHARLES L. CAMPBELL, OF BOSTON, MASSACHUSETTS, ASSIGNOR TO E.. B. B-ADGEB &4

SONS COMPANY, OF BOSTON, MASSAGE SETTS Usnfrrs, A CORPORATION or cnLomNa'rIoN Application led .Tune 15,

1 nated, hydrogen chloride, and lsome of the substance to be chlorinated -that is not chlorinated in itspassage through the chlorinating reaction and which it is desirable to return to the chlorinating reaction, it belng desirable to prevent the introduction of molsture into the chlorinating reaction because aqueous hydrochloric acid injurious to the equipment would be formed thereby. It chlorinated -products are returned to the chlorinating reaction those products will be converted into higher chlorides but such a result is extremely undesirable Where monochlorides are sought to be produced. Furthermore, undesirable olelins and decomposition products may be produced by returnmg chlorinated products to the chlorinating reaction. It is desirable therefore to remove chlorinated substances from the products of chlorination before returning any part .0f such products to thechlorinating reaction. Hydrogen chloride -is advantageously removed fromthe products of chlorlnatlon by Contactin the products with Waterv and thereby a sorbing the hydrogen chlorlde with the production of aqueous hydrochlorlc acid. Such treatment,.however, contamlnates With moisture the products of chlorination and any unchlorinated substance therein that is to be returned to the chlorinating step. It

is desirable, therefore, to remove from the i products of chlorination, prior to absorption therefrom of hydrogen chloride with water,

such substances to be chlorinated as are not I chlorinated in their irst passage through the I sowhich enter the hydrogen-chloride-absorp- 1927.,.s'eria1 No. 198,913. y

tion step contain a substancethat will form a lilm o'n/Water the complete absorption of hydrogen chloride and the. product-ion ofthat the'undesirable etl'ect of such a filmforming substance may be avoided by maintaining such -substance in vapor phasedur- Y ing the absorption operation. However, the simplest. known steps for maintaining filmforming substance in vapor phase during the absorption operation consist in regulation of the temperature at which absorption is carried out and in introduction of substances of high vapor pressure into the absorption apparatus, and the presence in the absorber of chlorinated substances having higher boiling temperatures than the unchlorinated substances Would make difficult or defeat an ef- :tort to maintain all film-forming substances in vapor phase in the absorber. It might be impossible to maintain some monochlorides in vapor phase and almost certainlyimpossible to keep higher chlorides in vapor phase at a temperature at which a quantity of absorption water producing acid of desired strength' would sut'ciently remove hydrogen chloride from the products of chlorination. It is desirable therefore to remove chlorinated substances from Athe products ot' chlorination prior to removal of hydrogen chloride therefrom. Residualconstituents of the products of chlorination passing from the operation whereinv hydrogen cholride is removed from such products by absorption with water, include some of the substance to be chlorinated, which was not chlorinated in its passage through the chlorinating reaction,

ysmall a fraction as possible of the unchlorinated substance passing 'from the chlorinating reaction because it becomes moisture laden through its contact with water.

. An limportant object of my invention is to provide a process and apparatus for the practice thereof whereby the disadvantages above set out may be avoided and the advantageous operation above described `may be. carried out in the chlorination of substances. To assist in the understanding of my invention there is shown diagrammatically in the lsgifgle figure of the drawing ap aratus emying my invention and where y my process may be racticed. In orderto simplify the description of my apparatus and of my process I will describe my invention in conncction with the chlorination of pentanes,l but it is to be understood that my invention is not limited to such operation but is applicable to the chlorination of other substances and is susceptible to all modifications in form and procedure which fall within the spirit of my invention.

A substance to be chlorinated, for example, a mixture of pentanes, maybe maintained in circulating tank 12 from which it is passed by pump 13 to vaporizer 14 which may be heated in any suitable manner as by the circulation of steam. The vapor of pentanes is then passed through ipe 15 into which chlorine vapor is intro uced by pipe 16 and the mixture passes to reactor 17 in which the reaction is caused by any desired agent, such as heat or light. From the reactor 17 the products of 'chlorination pass through pipe 18 to a cooler 18el from which the vapors, preferably cooled to a temperature corresponding to or above the saturation point thereof at the pressures employed, e. g., 85 C. under 15 pounds pressure in the chlorination of pentanes, are introduced into rectifying column 19. A reflux of pentanes, for example, is maintained in the reotifying column -19 by pentane passed from circulating tank 12A through pipe to the upper part of the rectifying column l19 by pump 50".

I have found that by introducing all of the vapors oi the chlorinating reaction into a rectifying column, substantially all of the chlorinated substance may be removed from the products of chlorination prior to the absorption of hydrogen chloride from those products preliminary to returning unchlorinated substances to the chlorinating step. If

the products of chlorination were cooled even enough to condense the chlorinated substances and permit the withdrawal of hydrogen chloride, alll prior to introduction of the chlorinated substances into a rectifier, the.

hydrogen chloridewould contain vapors of chlorinated substances and vapors of vunchlorinated substances and the eventual re.

operation would require the subsequent addition of an unnecessarily large amount of heat inthe'bottom of the rectiier'to reva rize liquids introduced therein. I have ound,

moreover, that in the chlorination of pentane, a careful rectification in the manner herein described is essential to the complete separation of amyl chlorides from the products of chlorination.

f 0 In the practice of my inventlon, the chlorl- 7 'hated substances and some unchlorinated substances are withdrawn from 'the rectifier through pipe 20 and passed to storage, being further cooled in a suitable cooler 20i if desired. Unchlorinated substances in the liquid in which as much as possible of the unchlorinated substance still remaining in the products of chlorination is condensed and withdrawn through pipe 22 to circulating tank 12. I have found, particularly in the chlorination of pentanes, that careful removal of chlorinated substances by rectification is essential in order that unchlorinated substances condensed in condenser 21 and passed therefrom to circulating tank 12 shall be sufficiently -free of chlorinating substances.

Vapors passing from condenser 21 through pipe 23 consist mainly of dry hydrogen chloride saturated with vapors of unchlorinated substances and they are introduced into any suitable absorber 24 to which water is supplied through pipe 24a and from which aqueous hydrochloric acid is. Withdrawn through pipe 25, the temperature in the absorber belnocontrolled by cooling water from pipe 24. apors passing from absorber 24 through pipe 26 consist-mainly of unchlorinated substance which may advantageously be returned to the chlorinating step and those vapors are vcondensed in condenser 29 and returned to circulating tank 12, being neutralized and dehydrated, if desired, prior to introduction into circulating tank 12.

Additional quantities of substance to be chlorinated may be introduced into circlilating tank 12 by pipe 2. f

Referring tothe chlorination of pentanes as a specific application of my invention, the mixture of pentane vapor and chlorine may be introduced into the reactor in the proportion of 15 to 20 parts of pentane vapor to each part of chlorine vapor and at to 75 pounds gauge pressure at to 85 C., being brought to 275 C. to 325 C. -in the reactor by means of a gas burner 17".v Then the products of chlorination may be cooled to C. to` 90 C. before they are introduced into the rectiying column. The pentane reiluxed to the rectiying column may be at .atmospheric temperature. The vapors passf ing the rectifying column 19 may have a temperature corresponding to the boiling point of pentane vat the presure employed `and the vapors passing from condenser 21 may have a temperature not substantially higher than .the temperature. of the cooling water.

While I have described in greatdetail my process and apparatus embodying my invention, I do not intend that my invention shall be limited to such details but intend that it' i substances, the process comprising subjecting the products o the chlorinating reaction to rectification prior to cooling the same to a temperature below-the saturation point thereof, and by cooling in said rectifying operation obtaining a liquid fraction containing organic chlorinated substances and a vapor fraction'substantiall'y free of organic chlorinated substances.

2. In vapor phase chlorination of organic substances, the process comprising cooling together the products of ythe chlorination reaction to a point not below the saturation point thereof, and then subjecting the vapors together to rectification and thereby producing, by additional cooling and by maintaining a reflux of the unchlorinated organic substances, a liquid fraction containing organic chlorinated substances and a vaporfraction substantially free of organic chlorinatedsubstances.

3. In vapor phase chlorination of organic substances, the process comprising subjecting the products o the chlorinating reaction to rectification prior to cooling the same to a temperature below the saturation point thereof, and by cooling in said rectifying operation and while maintaining a reflux of unchlorinatedorganic substances in said operation,

obtaining a liquid fraction containing oranic chlorinated substances and a vapor fraction substantially free of organic chlorinated substances.

4. In vapor phase chlorination .of organic substances, the process comprising subjecting the Vproducts of the chlorinating reaction to rectification prior to cooling the same to a temperature below the saturation point thereof, and by cooling and by maintaining a reflux of the unchlorinated organic 'substances in said rectifying operation obtaining a liquid fraction contaming organic chlorlnated substances and a vapor fractionsubstantially free of chlorinated or anic substances and containing hydrogen c oride, vand then re moving hydrogen chloride from the substances contained in said vapor fraction.

5. In vapor phase chlorination of organic.l

substances, the process comprising subjecting the products of the chlorinating reaction to rectification prior to cooling the same to a temperature below the saturation point therei of, and by cooling and by maintaining a reflux of the unchlorinated organic subst-ances in said' rectifying operation o taining a liquid fraction containing organic chlorinated substances and a vapor fraction substantially l :free of chlorinated organic substances and containing hydrogen chloride, removing unchlorinated organic substances from said vapor fraction, and then removing hydrogen chloride from the residue of said vapor frac tion.

6. In the chlorinationof pent-aries, the proc ess comprising' subjecting the products of the chlorinating reaction to rectification prior to cooling the same to a temperature below the saturation point thereof and thereby producing a liquid fraction of liquid-products con taining chlorine products derived from pentane and producing a vapor fraction substantially free ofchlorine products derived from pentane.

7. In'. the chlorination of pentanes, the

process comprising subjecting to rectification all of the products in the chlorinating reaction' prior to cooling the same to a-tempera-- i ture below the saturation point thereof while maintaining a reflux of pentane in said recti-- fying operationand thereby producing aliquid fraction containing'chlorine products derived from f entane and a vapor'fraction substantially ree ofv chlorine products derived from pentane.

l8. In the chlorination of pentanes, the process comprising subjecting to rectification all of the products inthe chlorinating reaction prior to cooling the same to a temperature below the saturation point thereof while maintaining -a reflux ofpentane in'said rectifying operation and thereby producing a 1i uid fraction containing chlorine products derived from pentane and a vapor fraction substantially free of chlorine products derived from pentane and containing hydrogen chloride, and then removing hydrogen chloridefrom the substances contained in vsaid vapor frac-4 tion.

- 9. In the'chlorinatio'n of pentanes,the process comprising subjecting to rectification all ofthe products in the chlorinating reaction prior to cooling the same to a temperature below the saturation point thereof while maintain-ing a reflux of pentane in said rectifying operation and thereby producing a liquid fraction containing chlorme products derived from pgptane and a vapor fraction substantially of chlorine products' derived from` ntane and containing hydrogen chloride an pentanes, withdrawing pentanes from the substances contained in said vapor -fraction, and then removing hydrogen chlos ride from the resulting residue.

10. In the chlorination of pentane, the process comprising subjectin to rectification all of the products in the chornating reac-`- tion prior to cooling the same to a temperlo. ature below the saturation point thereof while maintaining a reflux ofl entane in said Arectifying operation and there y producing a liquid fraction containing chlorine products derived from ntane and a vapor fraction substantially ee of chlorine products derived' from pentane, and containing hydrogen chloride, then removing hydrogen chloride from the substances contained in said vapor fraction and containing hydrogen chloride 20- and pentanes,' withdrawing pentanes from the substances contained in said vapor fraction,` then removinghydrogen chloride from the re- Y sulting residue and returning to the chlorinatingr operation the pentanes freed of hydrogen 25 ch oride.

In testimony whereo-I. have signed my name to this s cification:

( lleIARLES L. CAMPBELL. 

